Ammonium lignosulfonates

ABSTRACT

A method of producing ammonium salts of sulfomethylated lignins suited for use as dyestuff and coal-water slurry additives comprising of the steps of ionizing the phenol component of a lignin material by-product of the black liquor of a kraft paper-making process in an alkaline liquid medium, methylolating the lignin material, lowering the pH of the liquid medium to an acid pH to precipitate the methylolated lignin material, washing the precipitated lignin material with water to remove inorganic salts and residual reactants therefrom, and sulfonating the washed, purified methylolated lignin material with an ammonium salt of a sulfur-oxygen containing compound in a liquid medium. 
     The washed, purified methylolated lignin material is preferably sulfonated at an acid pH level to minimize the production of electrolytes when the lignin is to be used for dyeing at low pH. Lignin products produced by the method, as well as dye and coal-water slurry compositions containing such products are also disclosed.

This is a division of application Ser. No. 679,901 filed Dec. 10, 1984,abandoned.

The present invention relates to a method of producing ammonium salts oflignosulfonates and to products so produced thereby, and, moreparticularly, to ammonium lignosulfonate salts particularly suited foruse as a dispersant in dye compositions and aqueous coal slurries.

BACKGROUND OF THE INVENTION

It is known to employ lignosulfonate compounds, including sodium saltsof lignosulfonates, as an additive, such as a dispersant, in textiledyestuffs and printing pigments. Such lignosulfonate compounds aregenerally produced as a by-product of the wood pulping industry byeither the sulfite or kraft process. Such sulfonated lignin productsprovide three basic functions in dyestuff compositions:

(1) They assist in reducing the dye particles to a fine size;

(2) They maintain a dispersing medium for the dyestuff; and

(3) They are used as a diluent.

The advantages of employing sulfonated lignins as dispersants indyestuff compositions are based on their unique physical propertieswhich include good compatibility with many dye systems, outstandingdispersant characteristics at ambient and elevated temperatures, andavailability. There are certain disadvantages in employing lignins,whether they are sulfite lignins or sulfonated kraft lignins, asdispersants. Negative factors in the use of such lignins as dyestuffadditives relate to problems of high inorganic salt content, i.e.,electrolyte content, when lowered in pH, foaming, high pH, fiberstaining, poor heat stability, and high viscosity. These adverseproperties are troublesome to dyers and many attempts have been made toovercome these and other disadvantages.

Inorganic electrolyte content of lignin dispersants and dyestuffadditives greatly effect their use in a specific dyestuff additiveformulation. High electrolyte content of a lignin dispersant imposesunwanted side effects on hydrophobic dyestuffs. In vat dyes, high saltcontent of the lignin additives can cause harmful rheological effectsduring storage of the dyes. The viscosity of the oxidized form in thepresence of salts generally increases to a level where the dye mixturecan only be removed from a storage container with consideabledifficulty. Recent use in this country of double strength dyes overpowder dyes has necessitated a reduced application level of the lignindispersants in order to accomodate the increased amount of dye, thusdictating that the dispersant be in its purest state possible.

A number of technological developments have resulted in new methods andprocesses to modify sulfonated lignins to reduce the negative aspects ofemploying such materials as dye dispersants without simultaneouslycausing any major adverse effects upon those properties which rendersulfonated lignins desirable as dyestuff dispersants. The following U.S.patents are directed to reacting and modifying lignins to make them moresuitable as dye dispersants: U.S. Pat. No. 4,001,202 to P. Dilling etal., U.S. Pat. No. 4,184,845 to S. Y. Lin; U.S. Pat. No. 4,131,564 to P.Dilling; U.S. Pat. No. 3,156,520 to L. A. Baisdell; U.S. Pat. No.3,094,515 to K. F. Keirstead et al; U.S. Pat. No. 3,726,850 to Detroit;U.S. Pat. No.2,680,113 to E. Adler et al; U.S. Pat. No. 3,769,272 toHintz; U.S. Pat. No. 3,841,887 to Falkehag et al; U.S. Pat. No.4,355,996 to P. Dilling et al; and U.S. Pat. No.4,308,203 to Lin.

U.S. Pat. Nos. 2,525,433; 2,690,973; and 3,503,762 disclose the use oflignins as an additive in printing inks, pastes, and gels. The foregoingpatent art is cited to show the state of the art and is not

modifications for use as dye intended to be all inclusive of ligninmodifications for use as dye additives.

More recently in my copending commonly assigned U.S. patent applicationsSer. No. 601,047, now U.S. Pat. No. 4,521,336, and Ser. No. 601,049, nowU.S. Pat. No. 4,561,151, both filed Apr. 16, 1984, there is described aprocess for preparing sulfonated lignins particularly suited for use asdyestuff dispersants, and the products produced thereby, wherein theviscosity of sulfonated lignins can be reduced with improvement in heatstability properties by removing the low molecular weight component ofthe lignin and thereafter sulfonating the remaining lignin material withsodium sulfite (Na₂ SO₃) and aldehyde at a pH of about 8.0 to 9.2. Also,in my commonly assigned copending U.S. patent application Ser. No.532,677, filed Sept. 16, 1983 and now abandoned, there is disclosed aprocess for producing sulfonated lignins for use as dye dispersants andadditives, and the products produced thereby, wherein dispersability andheat stability of the lignins are improved by post-sulfonationcross-linking of the sulfonated lignins at controlled lower pH levels,typically a pH of between about 7.0 to 8.5.

In the paper industry, lignin is obtained as a by-product from spentpulping liquors, known as black liquor, where lignocellulosic materials,such as wood, straw, cornstalks, bagasse and the like are processed toseparate the cellulosic pulp from the lignin. The lignins employed inthe process of this invention may readily be obtained from the kraftwood pulping process wherein the natural lignin is present as a sodiumsalt. In kraft pulping, the wood is subjected to the effects of strongalkali. The lignin forms a soluble sodium salt in the alkaline regionwhich is separated from the cellulose and dissolves in the pulpingliquor. The lignin is then recovered from the black liquor byacidification.

Acidification of black liquor containing the lignin salt generally maybe accomplished by the introduction of carbon dioxide which converts thephenolic hydroxide groups on the lignin molecule, which are in ionizedform, into their free phenolic or acidic form. This conversion rendersthe lignin insoluble in the black liquor and, as a result, itprecipitates out. To precipitate the alkali lignins from the blackliquor as water-insoluble products, black liquor initially having a pHof around 13.0 is acidified to about a pH of 10.5 at which point thelignin begins to precipitate. The lignin precipitate can be furtherpurified by reducing the pH level to pH 2, where the lignin iscoagulated and washed with water to obtain a lignin product identifiedas "A" lignin.

Lignin obtained from the kraft, soda or other alkaline processes is notrecovered as a sulfonated product, but is sulfonated by reacting thematerial with a bisulfite or sulfite compound. A sulfonated lignin isunderstood to be any lignin containing at least an effective amount ofsulfonate groups to give water solubility in moderately acid and higherpH solutions.

One of the conventional processes for sulfonating lignin involvessulfomethylation of the alkali lignin by reacting the lignin with sodiumsulfite and formaldehyde. Such a process is described in Adler et alU.S. Pat. No. 2,680,113. Sulfomethylation acts upon the aromaticphenolic nuclei of the lignin molecule in such a manner that CH₂ SO₃ Hgroups are bonded to the aromatic phenolic ring. It is also possible tosulfonate the lignin side-chain of the aromatic nucleus by sodiumsulfite treatment of the lignin in the absence of formaldehyde.Sulfomethylation of the alkali lignin has been carried out generally ata pH level of 9.0 or higher, in order to ensure optimum phenolionization and solubility of the lignin for sulfomethylation.

Although prior art sodium salts of sulfomethylated lignins existed asrelatively pure products when sold as a high alkaline pH composition,their use as a dyestuff additive requires adjustment by a formulatorand/or a dyer to an acidic pH level commonly employed in most textiledyeing by the addition of acid. Since the amount of acid required toeither neutralize or acidify the lignin corresponds directly to theamount of electrolytes which develop in a given dyestuff formulation,acidification produces increased undesirable electrolyte content in thecomposition. In lowering the pH of the lignosulfonates, the phenolicgroups which convert from ionized form to acid form initially produce abuffering effect in the higher alkaline region, such that their initialresponse to acidification is minimal. This results in large amounts ofacid being necessary to initially lower the formulation pH when thestarting pH of the lignin compositions is in the higher alkaline range,resulting in the creation of corresponding higher amounts ofelectrolytes.

Acidification of the lignin by the formulator and/or dyer not onlyproduces undesirable salts in the dyestuff composition, but also is anadded expense in preparation of the lignin additive for use.

Although ammonium lignosulfonate salts have been produced as aby-product of the ammonia-based sulfite pulping process, and ammoniumnaphthalene sulfonates have been produced in the oil refining field,ammonium salts of sulfomethylated lignins have not heretofore beenproduced effectively as a commercially viable by-product from the blackliquor of the kraft pulping process. Such is due to the fact that whenan aldehyde, such as formaldehyde (CH₂ O), and ammonium sulfite [(NH₄)₂SO₃ ] are added under alkaline conditions to sulfomethylate the lignin,multiple reactions occur. In addition to forming a desired solubleammonium salt of the sulfomethylated lignin, ammonium hydroxide acts tocombine with the formaldehyde and the lignin to produce a large amountof undesirable insoluble monomeric, dimeric and trimeric ligninproducts.

These reaction products are illustrated by the following impericalformulae: ##STR1##

Attempts to produce the soluble ammonium salt of sulfomethylatedlignins, as described above, results in appreciable loss of the reactionmaterials in the form of insoluble polymeric lignin compounds.

Recent efforts have been directed in the energy field to the use ofcoal-water slurries as a fluid fuel to replace more costly oil and gasfuels commonly employed in power plant and boiler operations. Suchcoal-water slurries are made by grinding mine coal into a powder-likedust which is mixed with water and chemical additives to simulate fluidflow characteristics of conventional gas and oil fuels. The chemicaladditives in the coal-water slurries improve fluid flow characteristicsand assist, as a dispersant, to maintain the coal particles insuspension in the slurries. dispersants in coal-water slurries. U.S.Pat. No. 4,465,495 discloses the use of certain of such organosulfonatesalts in coal-water slurries. However, the sodium salts oflignosulfonates have been found to produce scaling and corrosion of fuelburners and boilers. Ammonium salts of sulfomethylated ligninby-products of the kraft paper-making process have not been producedwith sufficient economy to justify their use, due to the aforementionedcreation of an undesired insoluble lignin portion.

BRIEF OBJECTS OF THE PRESENT INVENTION

It is an object of the present invention to provide an improved methodfor manufacturing ammonium salts of lignosulfonates which overcomesproblems of the prior art.

It is a further object to provide an improved method for producingammonium salts of lignosulfonates particularly suited for use asdyestuff and coal-water slurry additives and dispersants.

It is a more specific object to provide as improved method of producinglow impurity and low electrolyte-containing ammonium lignosulfonatesalts as a by-product of a kraft pulping process.

It is still another object to provide improved lowelectrolyte-containing ammonium salts of lignosulfonates for use as dyecomposition and coal-water slurry additives.

SUMMARY OF THE INVENTION

The present invention is directed to a method of producing ammoniumsalts of lignosulfonate as by-products from the kraft wood pulpingprocess. The lignin compounds are particularly suited for use asdispersants in dyestuff compositions and in coal-water slurries. In themethod, the phenol component of the lignin material recovered from theblack liquor is ionized and methylolation of the lignin can occur in analkaline liquid medium; the pH of the liquid medium is lowered to anacid range to precipitate the methylolated lignin therefrom; themethylolated lignin is washed to remove inorganic salts, excess aldehydeand impurities from the lignin; and the lignin is thereafter sulfonatedwith an ammonium salt of a sulfur-oxygen containing compound in a liquidmedium at any desired pH level. The resultant lignin product, ifsulfonated at a neutral or acidic pH, may be employed directly as adyestuff additive without the need for large amounts of acid to acidifythe same, thus avoiding the formation of additional inorganic salts andincreasing the electrolyte content of the lignin, as in the prior art.

More specifically, in the present method, the phenol component of thelignin in liquid medium may be ionized, permitting methylolation of thelignin at a pH of between about 9.5 to 12.5, preferably at pH 11.0, bytreatment with an aldehyde, such as formaldehyde. The pH of themethylolated lignin is then lowered to a pH range of about 1.0 to 3.0 toprecipitate the lignin. The precipitated lignin is washed to remove theinorganic salts and unreacted formaldehyde therefrom. The methylolated,purified lignin composition thereafter is sulfonated with an ammoniumsulfite or bisulfite compound at any desired pH range without formationof the undesired insoluble monomeric, dimeric and trimeric reactionproducts, as in the prior art. Residues of such insolublenon-sulfomethylated lignin compounds present in the kraft ligninby-products produced in accordance with the present invention have beenfound to be consistently less than 0.1% by weight, based on the drylignin by-product weight. Preferably the sulfonation is carried out atpH of below about 7.0 if the lignin composition is to be employed as adispersant in a dye composition.

Low sulfonated lignin products of the present invention, i.e., ammoniumsalts of sulfomethylated lignins having a degree of sulfonation of about1 mole or less per 1,000 grams of lignin, may be produced to exhibit afree inorganic salt content, i.e., electrolyte content, of as low asbetween about 0.5 to 3.0%, based on the weight of solids in the lignincomposition. Lignin products of the present invention which have ahigher degree of sulfonation, i.e., a sulfonation of greater than about1.6 moles per 1,000 grams of lignin, have been produced to exhibit afree inorganic salt content, i.e., electrolyte content, at pH of.about7.0 of between about 5.0 to 13.0%, based on the weight of solids in thelignin composition.

In distinction thereto, certain known prior art high and low sulfonatedsodium salts of lignin products, i.e., REAX 83 and REAX 85 (products ofWestvaco Corporation) have been found to exhibit a 19 to 22% and a 14 to17% free inorganic salt content, respectively, at a pH of about 7.0.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The method of the present invention involves a five step procedure of(1) ionizing the phenol component of the lignin at an alkaline pH, (2)methylolating the ionized lignin by the addition of an aldehyde, (3)lowering the lignin pH to an acid pH to precipitate the methylolatedlignin, (4) washing the precipitate to remove undesired inorganic salts,unreacted aldehyde and any other residual reactants therefrom, and (5)thereafter sulfonating the methylolated lignin by the addition of anammonium salt of a sulfur and oxygen-containing compound, e.g., ammoniumsulfite or bisulfite, at any desired pH range. If the methylolatedlignin is sulfonated in an acid pH range, it may be used directly by adyer with little or no adjustment by acid or base to prepare it for thedyestuff composition.

Sulfomethylation of a lignin requires ionization of the aromaticphenolic ring for the reaction to occur. The ionization of the phenoliccomponent occurs when the lignin is subjected to an alkaline pH.Although the phenol component starts to ionize at a pH of approximately7.0, it is generally the practice to raise the pH of the lignin toapproximately 9.5 to 12.5 for optimum ionization. Heretofore, the ligninhas been sulfomethylated by the addition of both sodium sulfite andformaldehyde, resulting in a lignin product having a pH of approximately9.0 to 12.5 or higher. Such products then have to be acidified forsubsequent use by the formulator and/or dyer in a dyestuff composition,with consequent electrolyte build-up.

The new method of the present invention permits the production of anammonium salt of a sulfomethylated lignin at any desired final pH rangewithout formation of the undesirable insoluble products mentioned. Thisis because the ionized phenolic ring is only methylolated in thealkaline region, after which the methylolated lignin is converted to anacidic form to precipitate and wash the lignin to remove inorganic saltsand unreacted aldehyde therefrom. Sulfonation of the methylolated lignincan then be accomplished at any desired pH level without the undesiredside reactions and inorganic salt formation. For dyestuff end uses, thepH of the prepared sulfomethylated lignin can be readily available in anacidic pH range if desired by the dyer.

Thus, the present invention provides improved ammonium salts ofsulfomethylated lignins which have advantages over existing lignindispersants. The product can be produced as a kraft process by-productwithout the formation of undesired insoluble side reaction products. Aproduct pH of 7.0 or below can be achieved without large amounts of theinorganic salt and electrolyte interference as experienced with alkalineproduct pH of existing dispersants and additives. A lower conductanceand enhancement of lignin purity is achieved due to the marked reductionof side reaction materials and inorganic matter as a result of improvedlignin isolation and sulfonation. There is considerably lower acidrequirements for pH adjustments of the products to dyeing conditions.Lower lignin color and consequent reduced fiber staining is achieved asa result of lowering the sulfonation pH to a more desireable pH value.Improved heat stability of the product is achieved in use with dyeswhich are electrolyte sensitive. The present inventive method reactionmay be expressed as follows: ##STR2##

As can be seen from the foregoing chemical formulae, to avoid theundesired side reactions and reduce the electrolyte content of theresultant lignin composition, the lignin is acidified aftermethylolation to convert the phenolic group from its ionized to its acidform. After washing to remove inorganic salts, formaldehyde, andresidual reactants, the methylolated lignin is preferably acidified to apH of around 5.0, although any pH between 1.0 and 7.0 would besufficient for maintaining a final resultant pH of the dispersant at orbelow a neutral pH level. For dyestuff end uses, ammonium bisulfite (NH₄HSO₃) preferably may be used for sulfonation at a pH of around 6.3instead of ammonium sulfite [(NH₄)₂ SO₃ ]. A small change in pH from pH6.3 to pH 6.8 during the reaction is attributed to the small amount ofammonium sulfite present at a starting pH of around 6.3. If the ligninproduct is to be used as an additive in a coal-water slurry, alkaline pHproducts generally are desired. Thus the sulfonation reaction may becarried out in the alkaline range.

The following laboratory procedure illustrates one method of preparingthe sulfomethylated lignin products of the present invention. Althoughthe methylolation step employs three moles of formaldehyde, and threemoles of ammonium sulfite are employed for the sulfonation step (basedon 1,000 grams of lignin), other molar ratios of these components can beemployed with satisfactory results. For example, if it is desired tohave a lower sulfonation level, the amounts of the aldehyde and theammonium sulfur-oxygen containing compounds could be reducedaccordingly. The sulfonation step may be carried out at acid, neutral,or basic pH levels, as may be desired in the final product.

Laboratory Procedure A. Methylolation

(1) A known amount of solid lignin recovered from the black liquor of apulping process in "A" lignin form is slurried to a 25% total solidscontent.

(2) The pH of the slurry is adjusted to 11.0 with 50% sodium hydroxide(NaOH) solution.

(3) The temperature of the slurry is raised to 65 to 70° C.

(4) Three moles of formaldehyde (HCHO) are added and the slurry reactedfor two hours at 65° to 70° C.

(5) The resulting slurry is acidified to a pH of 5.0 with 25% sulfuricacid solution (H₂ SO₄).

(6) The precipitated lignin is heat coagulated to 85° C.

(7) The coagulated lignin is cooled to room temperature and the slurryfiltered through a Buchner funnel. collected solid lignin is washed witha volume of

(8) The collected solid lignin is washed with a volume of tap waterequivalent to the solids present therein (100 g. lignin to 100 ml. H₂O).

(9) The lignin solids content is determined, and a known amount ofmethylolated lignin slurry is adjusted to 25% solids.

B. Sulfonation

(1) Three moles of ammonium sulfite [(NH₄)₂ SO₃ ]are added to themethylolated lignin.

(2) The pH of the slurry is adjusted with ammonium hydroxide (NH₄₀ OH)to around 7.2 to 7.5, if necessary.

(3) The temperature of the slurry is raised to 95° to 100° C. and ismaintained for about 16 hours. Final pH should be approximately 8.4.

(4) The product is cooled and dried.

The sulfonation reaction can be conducted at atmospheric pressure at atemperature of around 80°-100° C., preferably at about 95° C., or atelevated pressures above 100° C. up to about 190° C., preferably atabout 120°-140° C. Atmospheric pressure conditions are tends to cause acolor preferred since pressure-reaction above 100° increase in thelignin product, the higher the temperature the darker the lignin color.This degradation or darkening in color reflects itself in higher fiberstaining characteristics during the dyeing cycle to produce duller colorshades.

Inorganic electrolyte contents of ammonium salts of sulfomethylatedlignin products produced in accordance with the foregoing laboratoryprocedure are determined by adding 10 grams of the lignin product to1,000 ml. of water. The pH is adjusted to 7.0 and the solution added toan Amicon Laboratory Ultra-Filtration System, Model M 2000 whichcontained a 500 molecular size membrane. The membrane allows molecularweights below 500, e.g., inorganic salts, to go through it while thelignin constituents are retained by the membrane. Nitrogen is used underpressure as a carrier gas. After the volume inside the ultra-filtrationapparatus decreases to 100 ml., deionized water is added to 1,000 ml.This sequence is repeated until the conductance of eluent correspondswith the conductance of the water. The concentrate inside theultra-filtration chamber is then removed, the water evaporated, and theresidue dried. The difference in the weight amount of the residue andthe 10 grams of lignin product orignally employed corresponds to theinorganic salt content and thus the amount of electrolyte by weightpresent in the sample.

A typical high sulfonated ammonium salt lignin product tested forinorganic electrolyte and salt content was found to have 5.2% by weightinorganic salt, or electrolyte, based on the weight of lignin solids,while a typical low sulfonated ammonium salt lignin product was found tohave 0.78% by weight based on the weight of lignin solids.

That which is claimed is:
 1. A dyestuff composition comprising a dye andas an additive therein an ammonium salt of a low-electrolyte containingsulfomethylated lignin having about one mole or less sulfonation per1,000 grams of lignin, an inorganic electrolyte content in an aqueousmedium of from about 0.5 to 3.0% by weight based on the dry weight ofthe lignin, and having a pH value of about 7.0.
 2. A dyestuffcomposition comprising a dye and as an additive therein an ammonium saltof a low-electrolyte containing sulfomethylated lignin having asulfonation of about 1.6 moles or greater per 1,000 grams of lignin, aninorganic electrolyte content of between about 5.0 and 13.0% by weightbased on dry weight of the lignin, and having a pH value of about 7.0.3. A dyestuff composition comprising a dye and as an additive therein anammonium salt of a low-electrolyte containing sulfomethylated ligninprepared by(a) ionizing the phenol component of a kraft lignin materialin an alkaline liquid medium, (b) adding formaldehyde to the liquidmedium to methylolate the lignin material at the ortho position of thephenol component, (c) lowering the pH of the liquid medium to an acid pHto precipitate the methylolated lignin material, (d) washing theprecipitated lignin material with water to remove inorganic salts andresidual reactants therefrom, and (e) sulfonating the washed, purifiedmethylolated lignin material with an ammonium salt of a sulphur-oxygencontaining compound in a liquid medium while maintaining the pH of theliquid medium at about 7.0 or below.
 4. The dyestuff composition ofclaim 3 wherein the methylolated lignin material is sulfonated at a pHof about 6.3.
 5. The dyestuff composition of claim 3 wherein the ligninmaterial is methylolated at a pH level of between about 9.5 to 12.5. 6.The dyestuff composition of claim 5 wherein the methylolation pH isabout 11.0.
 7. The dyestuff composition of claim 3 wherein the ligninmaterial is sulfonated by reaction with an ammonium sulfite or bisulfitecompound.